Endothermic reaction apparatus

ABSTRACT

An endothermic reaction furnace includes one or more elongated reaction tubes defining therein an endothermic reaction flow path and a combustion flow path for providing heat to drive the endothermic reaction. The combustion flow path is arranged so that fuel and combustion air are separately heated by the heat inside the furnace preferably to significantly above their autoignition temperature before being combined in a combustion zone where they mix, autoignite and burn. The fuel is introduced into the combustion zone by a plurality of tubes having outlet ends arranged to produce annular shrouds of flame around each reaction tube that are directed countercurrent to the endothermic reaction product.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of Ser. No. 08/700,794 filed Aug. 21,1996 (now abandoned); which is a division of Ser. No. 08/247,647 filedMay 23, 1994 (now U.S. Pat. No. 5,565,009); which is a continuation ofSer. No. 07/888,776 filed May 26, 1992 (now abandoned); which is acontinuation-in-part of Ser. No. 07/810,251 filed Dec. 19, 1991 (nowabandoned); which is a continuation-in-part of Ser. No. 07/504,375 filedApr. 3, 1990 (now abandoned).

BACKGROUND OF THE INVENTION

The present invention relates to apparatus used in conductingendothermic reactions, and particularly to furnaces for reforming lighthydrocarbons, especially mixtures of steam and/or carbon dioxide andlight hydrocarbons.

Hydrogen for use in anmonia synthesis, methanol synthesis orhydrocracking plants, is frequently produced in a process using thefollowing endothermic reforming reaction: ##STR1## The hydrocarbon canbe methane, which is shown in the above reaction, or other lighthydrocarbons, or mixtures of these such as natural gas. The samereactions may also be employed where the desired product is CO or bothCO and H₂. Another endothermic reaction is the conversion (pyrolysis) ofethane to ethylene which also produces the by-product hydrogen (H₂), andthis reaction requires heat only, usually about 950° C. and 3atmospheres pressure, but needs no catalyst. The catalyst over which themethane reaction is carried out is, for example, nickel on an inertsupport, such as alumina, and is contained usually in vertical tubeswhich are supported in a furnace frequently called a "reformingfurnace". Reforming furnaces are disclosed or schematically shown in theprocess flow diagrams of U.S. Pat. Nos. 3,132,010; 3,264,066; and3,382,044.

The tubes in the usual reforming furnaces extend vertically withreactants being fed by a manifold to one end of the set of tubes andproduct-rich gases being withdrawn from the other end of the tubes.Because the reforming reaction occurs at a high temperature and isendothermic, heat must be supplied to the tubes to heat the reactants.The reaction is carried out in the tubes at a high temperature of about1500° F. and at a pressure of about 150 to 450 psig.

Various efforts have been made to improve the performance of thereforming furnace or to improve the structure of the furnace tofacilitate the maintenance and operation of the furnace. For example,U.S. Pat. No. 4,161,510 to A. J. Edridge teaches the use of a ceramicpaint coating on the exposed surface of the reforming tubes in which thereaction is conducted, the paint being reflective to reduce fissurecreep of the tubes. U.S. Pat. No. 4,714,593 to A. Naito et al. teaches areforming apparatus which uses a catalyzed heat generating apparatus toachieve miniaturization of the furnace. U.S. Pat. No. 4,810,472 to S. P.Andrews et al. teaches a reforming apparatus which employs closed ended,double pass, externally heated, metal reformer tubes, also known asbayonet-tubes with controlled heat exchange between the product gasstream and the reactant stream across the wall of the tube.

Apparatus is also known which employs ceramic tubes for carrying out gasreactions in those ceramic tubes. For example, U.S. Pat. No. 2,987,382to F. Endter et al. discloses such a ceramic tube furnace. Further, U.S.Pat. No. 2,018,619 to F. Winkler et al. teaches tubes made from materialcontaining elementary silicon which may be embedded in other gas-tighttubes and which prevents carbon formation in carrying out pyrogenicconversion of hydrocarbons.

Known reforming furnaces are large and expensive, when measured as perunit of capacity, have tube lives shorter than would be desired, areprone to carbon deposition ("coking"), and must be frequently operatedat temperatures below the ideally preferred values (for most efficientreactivity) due to the creep and corrosion behavior of their reformingtubes.

Therefore, it is an object of the present invention to provide animproved apparatus for conducting endothermic reactions, such asreforming light-hydrocarbons, and which will provide improvedconversions, energy efficiency, and maintenance.

SUMMARY OF THE INVENTION

The present invention provides a unique furnace design in which the heatnecessary to drive the endothermic reaction is generated inside thefurnace by autoignition of a gaseous fuel and air. The flow paths ofendothermic reactant and product, on the one hand, and air and gaseousfuel and combustion products therefrom, on the other hand, are arrangedso that the air and fuel are separately heated by the heat generatedinside the furnace to above their autoignition temperature before beingcombined in one or more combustion zones where they autoignite andcombust. The flow paths are also arranged so that the combustion gasesas well as the endothermic reaction product are cooled before exitingthe furnace. By this means the need for separate ignition devices toinitiate combustion of the fuel/air mixture in each combustion zone iseliminated. This is particularly valuable in large-scale, multi-tubereforming furnaces, since it allows close packing of the combustiontubes and also eliminates costly downtime and repair efforts needed toservice inoperative ignition devices.

The inventive furnace is designed to have the endothermic reaction occuron the Inside of metallic reaction tubes, with the combustion of fueland air occurring outside the tubes. According to the Invention, anendothermic reaction apparatus for effecting an endothermic reactioncomprises:

a vessel, the vessel including an inlet port for an endothermic reactantto be subjected to an endothermic reaction to convert the reactant to anendothermic product, an outlet port for the endothermic product, and anexothermic reaction (combustion) chamber,

a plurality of reaction tubes providing flow passages between the inletand outlet ports, the reaction tubes extending through the exothermicreaction chamber from a downstream end to an upstream end of theexothermic reaction chamber,

first and second supply passages for separately supplying first andsecond exothermic reactants (fool gas and air) to the exothermicreaction chamber for exothermically reacting within the exothermicreaction chamber and for providing flow of exothermic reaction productsin a direction going from the upstream end to the downstream end of theexothermic reaction chamber, the first and second supply passagespassing through a preheating zone within the vessel wherein heat istransferred to the exothermic reactants from the endothermic reactionproduct for preheating the exothermic reactants prior to mixing andexothermically reacting and for cooling the endothermic reactionproduct, and

a plurality of feed tubes respectively associated with the reactiontubes and disposed to produce an annular shroud of flame around eachreaction tube, the feed tubes each having an outlet end located at theupstream end of the exothermic reaction chamber and oriented to directat least one of the exothermic reactants exiting therefrom in adirection substantially parallel to the reaction tubes such that theannular shroud of flame is directed countercurrent to the endothermicreaction product.

According to another aspect of the invention, a process for carrying outan endothermic reaction in an endothermic reaction apparatus in which anendothermic reactant is heated by exothermic reaction of two exothermicreactants to thereby convert the endothermic reactant into anendothermic product, comprises:

causing the endothermic reactant to flow through a plurality of reactiontubes wherein the reactant is to undergo the endothermic reaction, thereaction tubes extending through an exothermic reaction (combustion)chamber of a vessel from a downstream end to an upstream end of theexothermic reaction chamber,

removing the endothermic reaction product from the vessel after flowthrough the reaction tubes,

separately supplying first and second exothermic reactants (fuel gas andair) to the exothermic reaction flow path for reacting within theexothermic reaction chamber with the exothermic reaction productsflowing in a direction going from the upstream end to the downstream endof the exothermic reaction chamber, and

directing the first and second exothermic reactants into the exothermicreaction chamber for exothermically reacting and producing an annularshroud of flame around each reaction tube, said directing of one of thefirst and second exothermic reactants being effected by a plurality offeed tubes each having an outlet end located at the upstream end of theexothermic reaction chamber and oriented to direct such one exothermicreaction fluid exiting therefrom in a direction substantially parallelto the reaction tubes such that the annular shroud of flame is directedcountercurrent to the endothermic reaction product,

removing the exothermic reaction products from the vessel after passagethrough the exothermic reaction chamber, and wherein

said separately supplying step includes passing the first and secondexothermic reactants through a preheating zone within the vessel whereinheat is transferred to the exothermic reactants from the endothermicreaction product for preheating the exothermic reactants prior to mixingand reacting and for cooling the endothermic reaction product prior toremoval from the vessel.

According to a further aspect of the invention, an apparatus forcarrying out an endothermic reaction in which an endothermic reactantgas is heated by the combustion of air and a combustible fuel gasthereby to cause the reactant gas to form an endothermic product, whichapparatus comprises:

vessel;

a plurality of metallic reaction tubes in the vessel dividing theinterior of the vessel into a plurality of separate reaction tube flowpaths collectively defining a reaction flow path for carrying out theendothermic reaction and a plurality of separate elongated flame flowpaths outside the reaction tubes collectively defining a combustion flowpath, the reaction flow path and the combustion flow path being inthermal communication with one another so that heat in the combustionflow path can be transferred to the reaction flow path;

respective heat generating means associated with each of the metallicreaction tubes for generating heat by the combustion of fuel gas and airwith the resultant flames forming annular shrouds of flames around andextending along the reaction tubes;

an inlet port for causing the reactant gas to flow into the reactionflow path and an exit port for withdrawing endothermic product gas fromthe reaction flow path;

air and fuel gas supplies respectively adapted to separately supply airand fuel gas to each of the heat generating means, the heat generatingmeans being located in the interior of the vessel whereby the air andfuel gas can be heated to above their autoigniton temperature prior toreaching the heat generating means; and

an exit path for withdrawing combustion gas from the combustion flowpath; and

wherein the heat generating means are located at an upstream end of acombustion chamber in the vessel through which the metallic reactiontubes extend from a downstream end to the upstream end of the combustionchamber, and the heat generating means include a plurality of feed tubesrespectively associated with the metallic reaction tubes, the feed tubeseach having an outlet end located at the upstream end of the combustionchamber and oriented to direct the fuel gas exiting therefrom in adirection substantially parallel to the metallic reaction tubes suchthat the annular shroud of flame is directed countercurrent to thereactant gas/endothermic product.

The invention also provides a process for carrying out an endothermicreaction in the aforesaid endothermic reaction apparatus in which anendothermic reactant is heated by the combustion of air and acombustible fuel gas to thereby convert the reactant into an endothermicproduct, the method comprising:

via the inlet port causing the endothermic reactant to flow along theendothermic reactant flow paths,

via the air and fuel gas supplies separately feeding the air and thefuel gas to each of the heat exchanging means, the fuel gas and airbeing heated to above their autoignition temperature prior to reachingthe heat generating means so that the air and fuel gas autoignite andcombust to produce heat in the combustion flow path with the resultantflames forming annular shrouds of flames around and extending along thereaction tubes, the heat being transferred to the endothermic reactionflow paths thereby causing the endothermic reaction to occur,

via the outlet port withdrawing endothermic product gas from thereaction flow path, and

via the exit path withdrawing combustion gas from the combustion flowpath.

In a particular embodiment of apparatus according to the invention, thecombustion means preferably employs concentric air and fuel supplytubes, which are most preferably also concentric with the metallicreaction tubes. This arrangement allows for close-packing of the tubesas well as autoignition of the fuel/air mixture, both of which featurescontribute to a simple design and ease of operation.

The present invention will become more apparent from the followingdescription taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross sectional representation of the reforming apparatus ofthe present invention.

FIG. 2 is a cross sectional representation of the reforming apparatus ofFIG. 1 taken along lines 2.

FIG. 3 is a cross sectional representation similar to FIG. 2 but showinganother embodiment of the present invention.

FIG. 4 is a cross sectional representation, similar to FIG. 1, ofanother embodiment of the invention which uses a perforated fuel feedtube.

FIG. 5 is a cross sectional representation of yet another embodiment ofthe present invention, which uses a bayonet combustion tube.

FIG. 6 is a block diagram of a methane reforming process whichillustrates the present invention.

FIG. 7 is a cross-sectional representation of still another embodimentof the invention.

FIG. 8 is a graphic representation of the temperature profiles ofreaction and production gases as well as the combustion tube wall of theapparatus of FIG. 7 when in steady-state operation.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is described below in connection with a number ofpreferred embodiments. In one embodiment, which was described in myearlier application Ser. No. 07/504,375, filed Apr. 3, 1990, combustionis carried out inside of one or more ceramic tubes with the endothermicreaction being carried out in one or more reaction flow paths locatedoutside the combustion tubes. In another preferred embodiment describedbelow, the endothermic reaction is carried out inside of one or moremetallic reaction tubes with combustion occurring in one or morecombustion flow paths located outside the tubes. In both embodiments, asmore fully described below, the flow paths of the various reactant andproduct gases are arranged so that the combustion air and fuel areseparately heated to above their autoignition temperature before beingcombined in the interior of the furnace where they mix, autoignite andburn to provide the heat necessary to drive the endothermic reaction.

Ceramic Tube Embodiment

The reaction apparatus of this embodiment is shown generally at inFIG. 1. Although it is oriented vertically, it should be appreciatedthat it could be operated horizontally, and so is not limited to aparticular orientation. The apparatus comprises a steel shell 12 linedinside with a refractory insulation material 14 having a bottom plate 16(which may also be referred to as a tube sheet) sealed, by gaskets andbolting or the like, to the steel shell, and a top plate 18 (or top tubesheet), which together define the reaction vessel. The bottom plate 16supports a catalyst bed 20 through which passes one or more combustiontubes 30, which are made of a ceramic material and are sealed to bottomplate 16 and top plate 18. The shape of the reformer 10 is generallycylindrical and could be described as somewhat similar in constructionto a shell and tube heat exchanger. The ceramic burner tubes are sealedto plates 16 and 18 by a hollow screw (not shown) threaded into the tubesheet at the end of the tube in combination with a steel pressure ringwhich expands a graphite seal, preferably a graphite foil spiral wrappedannular cylinder seal (such as Grafoil brand foil from Union Carbide).These seals 32 will hold the combustion tube in place, and contain themuch higher shell side gas pressures, yet allow it to expand thermallyand individually without significant gas flow leakage past the seals.Also, it may be desirable to apply an axial compressive force or preloadto each tube, which will tend to neutralize or subtract from the axialtensile stresses produced by heat flows, by incorporating, e.g., in thetube seal assembly a stack of Belleville type springs (not shown) or thelike. Alternatively, the seals could be held in place by a device whichalso provides the axial compressive force. A feature of the presentdesign is that it allows for the use of lower temperature seals wherethe combustion tube or tubes are joined to the tube sheet.

Steel shell 12 has one or more feed inlets 22 for passing the feed gasmixture which is to be reformed into the reformer and down through thepacked bed 20 to exit through one or more product outlet(s) 24. The feedgas mixture, for example, may be a mixture of natural gas and steam ifthe endothermic reaction is methane reforming reaction, although themixture could be natural gas and water, which converts to steam in thereactor, or only natural gas, with the steam coming from water fedseparately into the reactor. As can be appreciated, other combinationsof feed mixtures can be introduced. As illustrated in FIG. 1, thecatalytic bed 20 which can be nickel on an alumina, inert support, orother appropriate catalyst, could include an inert section or zone 26,or the entire bed could consist of a single catalyst material or pluralcatalyst materials. In fact, the apparatus could be operated without acatalyst for some endothermic reactions.

Located concentrically inside combustion tube 30 is a fuel feed tube 34,which can be made from a metal alloy or a ceramic material. Fuel feedtube 34 is fixed to outer plate (or tube sheet) 35 by welding, or byusing an o-ring or graphite foil seal 37. Fuel is fed from inlet 36 intofuel inlet manifold 38 to fuel feed tube 34. Air is fed via air inlet 40to air inlet manifold 42 which is defined by outer plate 35 which isspaced apart from tube sheet 16 and which communicates with combustiontube 30 via annular inlet 44 so that air will flow in the space betweenthe outer wall of fuel tube 34 and the inner wall of combustion tube 30.The combination of combustion tube 30 and fuel feed tube 34, constitutethe heat generating means for the reactor.

The fuel gas is any clean fuel to which sufficient water vapor has beenadded (if necessary) to prevent coking prior to its combustion. If thefuel contains a high carbon level, it will require some preheating tomaintain the necessary humidity level without condensation.

A resistance heating coil 46 is used inside the outer shell wall orshell 12 of the reactor for cold starting the reactor. The resistanceheater will preheat the adjacent zone to approximately 600° C. (whichwill be more or less, depending upon the specific fuel being used), atwhich point auto-ignition of the fuel and air can occur. It may benecessary to flow air through until preheating is complete when the gascan be introduced to produce ignition in flame zone 50. The exhaust fromcombustion tube 30 is collected in exhaust manifold 52 and passes outexhaust outlet 54 which is in communication with manifold 52.

The ceramic combustion tube 30 is preferably made from sintered aluminaand can be made by any of the various available processes for making andshaping dense (impervious) ceramic bodies. Also, there is no criticalityin the use of alumina and other ceramic compositions can be used. Forexample, U.S. Pat. No. 4,346,049 to J. A. Coppola et al. teaches asilicon carbide composition and process for producing sintered alphasilicon carbide ceramic bodies, the teachings of which are incorporatedherein by reference, and such could be used to make the ceramic tube.Other ceramic compositions that could be employed include siliconnitride, aluminum nitride, sialon, or the like. The exact materialpreferred will depend upon the reactants and reaction products involvedin the process, as well as temperature and pressure conditions.

The steel shell 12, bottom plate 16, top plate 18, manifolds 38 and 52,and outer plate 35 are preferably made of conventional pressure-vesselsteel which is designed and rated for the reformer internal pressure ofup 1200 psi or more and for temperatures of up to about 350° C. Therefractory insulation 14 is preferably an erosion-resistant,low-conductivity type insulation such as an alumina composition withexpansion joints used as required. The refractory should be rated for atleast 1300° C. continuous duty.

FIG. 2 shows a cross section of reformer 10 along lines 2--2 in FIG. 1.As can be seen fuel tube 34 is located concentrically within combustiontube 30 which in turn is surrounded by catalyst bed 20 inside insulatedsteel shell 12. The heat from combustion tube 30 will be transferredinto catalyst bed 20 for effecting the endothermic reaction to reformthe mixture of steam and light hydrocarbons. The use of externalpressure surrounding the combustion tube 30 has the very significantadvantage of placing the tube in a compressive stress state, whereceramics are much stronger than they are in tension.

As shown in FIG. 3, the design could consist of more than one burnertube with FIG. 3 illustrating seven burner tubes in an appropriatepattern. The invention is not limited to the use of one or seven, and iscontemplated that as many as many thousands of combustion tubes could beincorporated in an appropriate size reformer apparatus. The use ofsmall-diameter ceramic combustion tubes and graphite foil sealsfacilitates a denser packing of burner tubes than has been previouslyavailable in prior art apparatus.

The air supplied to inlet 40 could be supplied by a blower or acompressor depending upon the desired pressure drop, heat transferrequirements, and operation employed. A compressor will generate ahigher inlet pressure than a blower, however, the cost of operating ablower would be less than operating a compressor. Also, it may bedesirable to preheat the air fed to the heat generating means. Althoughno preheater is illustrated, such devices are known in the art and arecommercially available. If desired, the exhaust flow could be expanded(with possibly some added heat) through a gas turbine to drive the aircompressor.

The apparatus shown in FIGS. 4 and 5 are basically similar to that shownin FIG. 1 in that they include the shell 12, which contains a catalystbed 20, and has feed inlet 22 and product outlet 24. The difference inthese embodiments lies in the design of the heat generating means,although in each case, it is enclosed by the reaction vessel.

As shown in FIG. 4, combustion tube 30 has a feed gas tube 60 which hasperforations or holes 64 at spaced intervals along its length and hasone end 66 plugged or otherwise closed. In this way, fuel fed via inlet36 into manifold 38 will pass down tube 60 until it exits via theperforations 64. When the reactor is at its operating temperature, thefuel will mix with the air fed via inlet 40 to manifold 42 and into theburner zone 68 and auto-ignite to heat the reactor. Note that plug 66need not resist very hot temperatures and thus could be made of graphiteor heat resistant organic cement. Other methods for the stagedintroduction of the fuel could also be employed.

The design in FIG. 5, differs in that the heat generating means is abayonet type heat generating means. In this design, the tube sheet isreplaced by an insulated vessel closure 70 and the combustion tube is aclosed end tube 80 sealed to plate 18. The combustion tube is shown witha closed end but it could be a plugged design as shown in FIG. 4. Thefuel is fed via fuel inlet 82 to fuel feed tube 84, while air is fed viaair inlet 86 to air feed tube 88. At operating temperature, the fuelwill auto-ignite in flame zone 90 to produce the heat for conducting theendothermic reaction. The exhaust gases will pass up combustion tube 80,as shown by arrow 92 to manifold 52 where they exit the apparatus viaexhaust line 54.

In general, for the apparatus of this embodiment, the combustion tubesrequire a length to inside diameter ratio of typically 500 to 700 inorder to achieve the required heat transfer per unit of flow volume fora natural gas plus steam reforming application. Even higher ratios areneeded, if the reactor is to operate with low temperature differentials.

The preferred tube separation distance in this embodiment is quitesmall; for example 0.3 to 0.5 inches. It is limited by the requiredsizes of the seals and their associated threads and the need to havesome small distance between these threads. Small distances lead tosmaller vessel sizes and improved shell-side heat transfer.

The number of tubes in a single reactor could be as few as one to asmany as 10,000 or more. Larger reactors will require thickerpressure-vessel walls, but will save on installation costs. Thepreferred tube wall thickness will depend upon tube strength, corrosionrates, and diameter. The use of external pressure will permit the use ofrelatively thin walls, since ceramics are much stronger in tension thancompression.

The preferred combustion tube inside diameter is usually equal to thetube separation distance (expressed as inside tube to inside tubesurface). Thus, if the separation distance were 0.4 inches, thepreferred tube ID would be 0.4 inches for a centerline spacing of 0.8inches. An equilateral triangular tube-arrangement is preferred formaximum packing density.

For example, one design could use 10,000 tubes, each 0.4 inch ID×0.5inch OD×20 feet long on 0.8 inch triangular pitch. The bundle diameterwould be about 7 feet and the total inside-surface area would be about20,900 square feet.

The base-case design of this embodiment employs a fuel and air streamentering the reactor at the same end where the process gas exits andflowing countercurrent to the process gas, with the exhaust leaving atthe opposite end, where the process feed enters.

Another variation would arrange cocurrent flow of combustion gases andprocess gases. This scheme would require a hot seal on the exhaust endof the ceramic tubes. Such a seal might be made of fused glass or aceramic cement, for example. The cold-end seal could be an O-ring orgraphite foil type to allow tube thermal expansion.

Closed-end, triple-concentric combustion tubes might be used, with thecombustion gas exiting at the same end of the reactor where the air andfuel enter. This is illustrated in FIG. 5. The open ends of theseconcentric tubes might be at either the process feed or at the processexit end of the reactor.

The upper operating temperature of the graphite foil seals is limited byoxidation by the air present on one side. If a controlled very slowleakage of process gas is permitted to occur through the seal, thiscould sweep this air away from the seal material and permit the seals toexhibit long life at higher temperatures. Such an arrangement may betermed a purged seal condition.

The reactor maximum process temperature can vary widely, as required.However, if the auto ignition condition is to be maintained, reactorsusing maximum process temperatures below about 500° C. (depending uponthe choice of fuel) will normally require the selection of one of theclosed-end combustion tube variants. In these cases, the maximum processtemperature could be as low as perhaps 100° C.

The combustion tubes might be made of various ceramics, depending uponthe service conditions (temperature, corrosion, stresses, etc.). Inaddition to alumina, other possible materials for some applicationswould be carbide ceramics such as silicon carbide or other oxideceramics such as mullite, stabilized zirconia, or the like. The use ofexternal pressure will be a major advantage in controlling the combinedstresses in the ceramic tubes to acceptable levels. Still othermaterials are also possible, such as metal tubes for lowertemperatureapplications.

If the fuel chosen is a mixture of a hydrocarbon (such as natural gas)plus steam, a reforming catalyst might also be positioned within thetube 34 to cause the fuel to partially reform during its heatup andhence to both absorb more heat from the process gas (improving cooling)and to simultaneously increase the heating value of the fuel gas(improving heating).

The following example is presented to illustrate the operation of anapparatus in accordance with Ceramic Tube Embodiment of the presentinvention and the advantages of very high temperature operation inproducing syngas of superior composition. Modifications of the physicaldimensions will alter the operating parameters and so adjustments may benecessary to achieve the same results.

The flow diagram shown in FIG. 6 is presented to help understand theexample presented here end the various parameters involved in theprocess of the present invention.

EXAMPLE 1

A feed containing 2.5 volumes steam plus 1.0 volume natural gas, (withan assumed composition of 90 volume percent CH₄, 7% C₂ H₆, 2% N₂, and 1%CO₂) is passed through either a conventional reformer or this invention.The conventional reformer is similar to that described by Dwyer et al.(U.S. Pat. No. 3,132,010) with a hot-zone reaction pressure of 155 psia,whereas the example of this invention uses 1070 psia for this pressure.The computed syngas compositions listed in Table 1 are based uponthermodynamic equilibrium compositions at the above pressures and attemperatures 20° C. below the stated Table 1 peak temperatures. Thecompositions are tabulated after condensing water to 40° C.

                  TABLE 1                                                         ______________________________________                                        Computed Syngas Compositions                                                                    Conventional                                                                  Radiant  This                                                                 Reformer Invention                                          ______________________________________                                        Reformer Peak Temperature (° C.)                                                           850        1170                                           Dried Syngas Pressure (psia)                                                                      140        1140                                           Dried Syngas Composition (mole %)                                             H.sub.2             72.49      74.13                                          CO                  15.97      20.56                                          CO.sub.2            6.83       3.77                                           CH.sub.4            3.60       0.96                                           N.sub.2             0.50       0.48                                           H.sub.2 O           0.61       0.10                                           Volume Dried Syngas/Volume Nat. Gas                                                               3.98       4.15                                           Percentage Methane Conversion                                                                     84.1       95.6                                           ______________________________________                                    

Based upon data from Table 1, the advantages of the apparatus of thepresent invention are that the syngas pressure is much higher, thuseliminating or reducing the need for syngas compressors, the methaneconversion percentage is much higher, the syngas CO/H₂ ratio is muchhigher, and the syngas CO/CO₂ ratio is much higher.

The new process may, if desired, be operated at still highertemperatures to obtain still higher methane conversions, CO/H₂ ratios,and CO/CO₂ ratios. It may also be operated at either higher or lowerpressures and/or steam ratios. The ceramic tubes are less prone tocoking than are metallic tubes under conditions of low steam ratios.

The new invention allows very high rates of heat transfer per unit ofreactor vessel volume. For example, the average rate of heat exchangebetween the process gas and the air/fuel/exhaust flow was calculated tobe some 7 MW/m³ for the reformer internal volume for a reformer designin accordance with the present invention and based upon the statedexample, and this figure is more than a factor of ten above thecorresponding value for a typical radiant reformer.

Metallic Reaction Tube Embodiment

As shown in FIG. 7, the inventive reaction apparatus of this embodiment,generally indicated at 100, comprises an elongated vessel 102 withexpansion joint 103 (e.g. a metal bellows) and defining a first end or"head" 104 and second end or head 106, ceramic fiber insulation 107 andan interior 108. For cold starts, an external burner (not shown) isemployed to preheat the incoming air to a temperature on the order of550° C. in order to preheat the reactor to above autoignitiontemperatures. This burner is shut off following the fuel ignition.

Within interior 108 is an endothermic reaction tube 110 which is securedto end plates or "tube sheets" 109 and 111 by suitable seals such as,for example, welding (not shown). As can be seen from FIG. 7, tubesheets 109 and 111 are rigidly secured to the walls of vessel 102 sothat the tube sheets are not axially moveable in said vessel relative tothe portion of the vessel to which they are attached, this being knownin the art as a "fixed tube sheet design." Furthermore, in the specificembodiment described there is no support structure, such as rods orbaffles, on the shell side of the vessel interior to support reactiontube 110 at an intermediate position (i.e. at a position intermediateits two ends) as is used in conventional designs to prevent lateralmovement of the tube and hence buckling under various compressive loads.

The inside of reaction tube 110 defines an endothermic reaction flowpath for carrying out the endothermic reaction, while the volume outsideof reaction tube 110 defines a combustion flow path for carrying outcombustion. Reaction tube 110 is filled with an endothermic reactioncatalyst 112 of a suitable shape and size. In the embodiment shown,catalyst 112 is composed of spheres approximately 5 mm in diameter. Inorder to foster heat transfer and thereby reduce thermal degradation ofreaction tube 110, endothermic catalyst 114 contiguous to combustionzone 116 is smaller in size, for example 3 mm in diameter. Inertmaterial 122 and 124 is provided on either side of endothermic catalyst112/114, also to improve heat transfer.

Head 104 and tube sheet 109 together define an inlet manifold 126 forreceiving endothermic reactant feed from inlet 128. Head 106 and tubesheet 111 together define an outlet manifold 130 for dischargingendothermic product through outlet 132.

Air header 134 together with tube sheet 111 define air manifold 136 forreceiving air from inlet 138. Air tube 140, which is concentric withreaction tube 110, communicates with air manifold 136 for charging airinto combustion zone 116 via annulus 142. Fuel header 144 together withair header 134 define fuel manifold 146 for receiving gaseous fuel fromfuel inlet 148. Fuel tube 150, which is also concentric with reactiontube 110 and air tube 140 communicates with fuel manifold 146 forsupplying fuel to combustion zone 116 via fuel annulus 152. Combustiongas header 154 together with tube sheet 109 define combustion gasmanifold 156 for discharging combustion gas produced by the combustionof fuel and air in vessel interior 108 through combustion gas annulus162, which is formed by reaction tube 110 and discharge pipe 160concentric therewith, and combustion gas outlet 158. As shown in FIG. 1,air tube 140 and fuel tube 150 are so configured that combustion zone116 is located in the interior of vessel 102 and, as further describedbelow, spaced far enough away from the reaction and combustion gasoutlets so that both the endothermic product gases and the combustionproduct gases will be considerably cooled before exiting the vessel.

In operation, once steady-state has been reached, endothermic reactant,such as a mixture of methane and water vapor, is charged into inlet 128,endothermic product is withdrawn from outlet 132, fuel and air arecharged into fuel inlet 148 and air inlet 138, respectively, andcombustion gases are withdrawn from combustion outlet 158. This sets upa countercurrent flow between the reaction gases flowing throughcombustion tube 110 and the combustion gases flowing through interior108 of vessel 102. The flow rates of the various reactants and productsand the size and shape of the various tubes are so selected that whenair and fuel are mixed in combustion zone 116 they will be at or abovetheir autoignition temperature. By this means, they will mix, ignite andcombust without the need for a separate igniter such as a glowplug,sparkplug or the like. Countercurrent flow of the endothermic reactantgases and combustion gases also tends to improve heat transfer betweenthe reactant gases and combustion gases on opposite sides of thereaction tube walls. This in turn minimizes hot spots and leads to alonger useful life of the tubes.

This beneficial effect is illustrated in FIG. 8 which is a graphicrepresentation of the temperature of various process gases as well asthe tube wall surfaces of reaction tube 110 of the apparatus of FIG. 7.In FIG. 8, the abscissa is a measure of the distance from combustionzone 116, with zero being taken as the start of combustion zone 116. Theordinate is a measure of the temperature of the various gases and tubewall being measured. In this figure, 164 indicates the endothermicreactant temperature profile, 166 indicates the endothermic producttemperature profile, 168 the fuel temperature profile, 170 the airtemperature profile, 172 the flame temperature profile, 174 thecombustion gas temperature profile, 178 the reaction tube outside walltemperature profile and 180 the reaction tube inside wall temperatureprofile. 182 indicates the boundary between inert 122 and endothermiccatalyst 112, while 184 indicates the autoignition temperature of thefuel/air combination.

As can be seen from the figure, even though the flame temperature of thecombusting gases reaches a very high level, the inner and outer tubewalls of reaction tube 110 stay relatively low, thereby remarkablyprolonging the useful life of these tubes and enabling metallic ratherthan ceramic tubes to be used in high temperature applications. At thesame time, the various gases exiting the device, both the endothermicproduct gases and the combustion gases, are cooled to reasonabletemperatures while inside the inventive furnace, the combustion gasesare heated to above their autoignition temperatures and at the same timesufficient heat is provided to the endothermic reactants to drive thedesired endothermic reaction. Also, the problem of high thermal stress,which can sometimes be experienced with ceramic tubes, has been avoided.

As more fully described below, the design features appropriate for thismetallic reaction tube embodiment of the invention are the same as, orsimilar to, those described above for the ceramic tube embodiment.However, for this embodiment, it is preferred that the tube separationdistance in the case of a multitube design be quite small. Preferably,the centerline spacing between adjacent tube groups (i.e. feed tube 150,air tube 140 and reaction tube 110) is 1.25 times the outside diameterof feed tube 150. Small distances lead to smaller vessel sizes. Also,tubes made from ceramics or other materials instead of metals can beemployed in this embodiment as well. However, metallic tubes arepreferable to ceramic tubes in this embodiment due to their greateravailability in long length to diameter ratios, ductility, ease ofsealing (by welding), reliability, lower cost, and thermal stressresistance.

The inventive reaction apparatus of this embodiment is ideally suitedfor large-scale operations such as the commercial production ofsynthesis gas by the steam reforming of gaseous hydrocarbons, especiallymethane. Steam reforming reactions are favored by higher temperatures,such as for example 800 to 1000° C., more preferably 870 to 920° C.,while most downstream uses of syngas, for example methanol synthesis andFischer-Tropsch synthesis, are favored at high pressures, such as forexample at least 10 atm, preferably 20 to 60 atm, more preferably 30 to50 atm. Therefore it is desirable to operate at these high pressures, atleast on the shell side, and high temperatures when carrying out thistype of reaction.

Large-diameter reaction tubes intended for large-scale furnaces to beoperated at these high temperatures and pressures, whether such tubesare made from ceramic or the expensive metal alloys needed to withstandsuch high temperatures, require very thick walls and exhibit poortemperature profiles internally. They are also very expensive. Thereforelarge-scale furnaces intended to carry out steam reforming at these hightemperatures and pressures must be made from a large number of long,small diameter closely-packed tubes to be economic. Close packing of alarge number of small diameter tubes is made possible by the presentinvention in this embodiment because the tubes are metal, the reactionoccurs inside the tubes and the autoignition of combustion gaseseliminates the need for igniters and/or flame holders to assure stablecombustion flames. The absence of a tube support structure inside thevessel on the shell side, which is a preferred but not mandatory featureof this embodiment, also helps.

In this connection, it is important to note that when the apparatus ofthis embodiment is operated with a pressure higher than atmospheric onthe tube side, such as in an integrated process involving methanereformation as a first step followed by further downstream high pressureprocessing, the tubes will be kept in tension. This is because thepressure on the tube side creates an axial force tending to push headers104 and 106, and hence inlet and outlet manifolds 126 and 130, apart andfurther because expansion joint 103 prevents the walls of vessel 102from providing any countervailing tensile force. Tension on the tubes isan important feature of this embodiment of the invention because thetubes, especially when long, thin tubes are used as is necessary foreconomic operation, have comparatively little strength in compressionand therefore any significant compressive load, axial or lateral, wouldrender the tubes unserviceable through buckling and distortion. Tensionon the tubes, however, gives the tubes added strength to avoid thebuckling problem, and thereby allows the tubes to be made thinner andhence cheaper.

Moreover, at the high temperatures encountered in most endothermicreactions, the tubes will inherently undergo creep, i.e. hightemperature deformation, primarily in the axial direction. For example,it is estimated that tubes approximately 25 feet in length will undergoan elongation of approximately 3 inches in a typical methane reformingenvironment. Axial creep deformation of the tubes allows the tubes toautomatically distribute the axial load evenly among all the tubes,which is quite different from conventional fixed tube sheet shell andtube heat exchangers in which tubesheet bowing causes the axial loads inthe tubes to vary considerably across the tubesheet. This automaticdistribution of the axial load evenly across the tubes contributes tothe longer useful life of the apparatus as a whole, since it avoidsearly failure of tubes subjected to disproportionately higher axialloads as would occur in prior art designs.

Thus, in a preferred mode of this embodiment, the present inventionprovides combustion furnaces having at least 100, preferably at least500, more preferably at least 1,000 or even 5,000 combustion tubes, eachhaving an inside diameter to length ratio of 50 to 1000, preferably 150to 500, more preferably 250 to 350.

In particular, the present invention is ideally suited for the design oflarge volume, high capacity furnaces having at least 100 combustiontubes, each with a length to internal diameter ratio of at least 100.Such furnaces are suitable for high temperature (at least 850° C.) andhigh pressure (at least 10 atm) operation. More preferred are furnaceshaving at least 500 combustion tubes each with a length to internaldiameter ratio of at least 200. Even more preferred for high volumeoperations are furnaces having at least 1,000 tubes, each with a lengthto internal diameter ratios of at least 250. These latter furnaces areespecially useful for high volume operations carried out at elevatedpressures, e.g. at least about 500 psi and elevated temperatures, e.g.at least about 875° C.

The following example is provided to more thoroughly illustrate themetallic reaction tube embodiment of the present invention:

EXAMPLE 2

A feed of the composition shown below is supplied to the FIG. 7apparatus at 350° C. and at the pressure and flowrate shown. The productgas composition was computed based upon chemical equilibriumthermodynamics at approximately 893° C. and 522 psia. The product exittemperature is 490° C. The air feed rate is 2139 kmol/hr at 120° C. and131 psia. The fuel gas contains 82% H₂, balance several other gases. Thefuel and air preheat temperatures are near 850° C. and the exhausttemperature is about 495° C.

    ______________________________________                                        Mole %          Feed Gas Product Gas                                          ______________________________________                                        H.sub.2         1.19     45.28                                                CO              --       14.93                                                CO.sub.2        8.18     5.66                                                 CH.sub.4        30.86    6.86                                                 N.sub.2         6.29     4.35                                                 H.sub.2 O       53.57    22.90                                                Pressure (psig) 638      508                                                  Flow Rate (kmol/hr)                                                                           3222     4583                                                 ______________________________________                                        Reformer peak process temperature:                                                                     900° C.                                       Combustion Tube Count:   1700                                                 Combustion Tube Inside Diameter:                                                                       19.8 mm                                              Combustion Tube Overall Length:                                                                        7260 mm                                              Combustion Tube Length/Diameter:                                                                       367                                                  ______________________________________                                    

This shows that high methane conversions to syngas can be achieved atdesirable high pressures and also at temperatures low enough toaccommodate many commercially available high temperature alloys. Thismeans that the inventive furnace can be made with metal, rather thanceramic tubes, and that these metal tubes will give long useful liveseven though used to provide high conversion of methane to syngas at highpressures.

General Description Applicable to Both Embodiments

Determining the best design and operating conditions of the inventivefurnace for a particular application depends on many factors asdiscussed below. For example, steam-methane reforming (and most of theother endothermic reactions of interest here) is favored by hightemperatures and by low pressures. However, most applications for theproduct syngas require that the syngas be at high pressure. The use ofcompressors to compress syngas is very expensive in both capital andenergy.

This invention makes it practical to produce syngas at any desiredpressure up to about 60 atm with metallic tubes and up to 100 atm ormore with ceramic tubes. The preferred pressure would be the lowestneeded for the subsequent uses of the product gas which, of course,means that the syngas compressor needed in prior. art arrangements canbe totally eliminated.

The pressure of the air, combustible fuel and combustion products in thecombustion flow path can be ambient as is conventional. Where theendothermic reaction is carried out at elevated pressure, however, it isdesirable to maintain the pressure of the combustion gases at a higherpressure, for example 2 to 10 atmospheres or more, since this reducesstresses on the reaction tubes and thus enables the reaction tubes to bethinner.

The preferred inside diameter to length ratio of the combustion andreaction tubes depends upon the embodiment selected, the approachtemperatures desired, and the allowable gas pressure drops in theparticular application. For example, the FIG. 1 embodiment willtypically employ an L/D ratio of 400 to 600 while the FIG. 7 versionwill preferably employ an L/D ratio of 250 to 350.

The preferred inside diameter of the combustion and reaction tubes isrelatively small, for example 5 to 50 mm, preferably 15 to 30 mm, foreconomic reasons, although tubes of any inside diameter could be used. Asmall diameter requires a thinner wall than a larger diameter for thesame temperature and differential pressure and is hence less costly. Ifthe tubes are too small however, the tube count will become very largeand costs will rise again. Also, very small diameters may cause catalystpacking problems for designs having catalyst inside the tubes, leadingto locally poorer heat transfer. For the ceramic tube embodiment inwhich combustion occurs inside the combustion tubes, very smalldiameters cause enhanced flame-zone heat transfer, which may causeexcessive wall temperatures. Larger tubes will exhibit unfavorableradial temperature gradients.

In determining the preferred tube count, a choice must be made between asingle very large reactor and multiple smaller reactors, especially forindustrial processes intended to treat very large volumes of processgas. In general, there are few overall cost advantages in using morethan several thousand tubes in a single reactor. The preferred minimumtube count is that needed to process the required throughput of gas.Using the FIG. 7 embodiment with a reaction tube inside diameter of 0.8inches, the synthesis gas production per tube in one example was about2.7 kg-moles/hour.

Preferred metal alloys for use in the inventive reaction furnace musthave high hot strength (resistance to creep and creep rupture) and highresistance to both oxidation and to process gas corrosion. Among thealloys suitable for typical applications are various nickel-based,high-temperature alloys. For example, if the inventive reaction furnaceis intended to be used for steam reforming of methane high temperaturenickel-based alloys containing chromium, tungsten and molybdenum, suchas Haynes® 230 (22% Cr, 14% W, 2% Mo balance Ni) available from HaynesInternational, Inc. of Kokomo, Ind., are preferred. If desired, metaltubes can be provided with suitable coatings to prevent metal dustingand other forms of attack. Such coatings are well-known in the art,alonizing being a specific example.

The preferred peak process temperature depends upon the pressure chosen,the tube material, the feed mixture composition, and the requirements ofexternal processes. It is often desirable to operate at the highesttemperature which will give acceptable tube life under the chosenconditions. In these cases, ceramic tubes might be operated at peakprocess temperatures from about 1050° C. to as high as 1200° C, whereasmetallic tubes may preferably be operated in the range of about 850° C.to 1000° C. In other cases, a superior process heat balance and overallcost savings will be obtained at somewhat lower temperatures than theabove, with the preferred peak process temperature for metallic tubesthen being about 875 to 925° C.

In a particularly preferred embodiment of the invention, the inventivereaction furnace is designed and operated so that during steady stateoperation the difference between the temperature to which the fuel andair are heated prior to mixing in the combustion zone and the maximumendothermic reaction temperature, which is indicated by temperaturedifference Δ in FIG. 8, is less than 200° C. Preferably this differenceis 50 to 100° C. Since most of the common gaseous fuels autoignite withair at temperatures of about 400 to 450° C., and since most endothermicreactions of interest here occur at approximately 850° C. to 950° C.,this means that in normal operation according to this preferredembodiment the air and gaseous fuel will be heated to significantly (400to 500° C.) above its autoignition temperature before being combined incombustion zone 116. This extensive heating results in extensive coolingof the endothermic product gases.

In the same way, it is desirable to design and operate the furnace sothat the combustion product gases are cooled significantly beforeexiting the furnace. By proper design and operation of the furnace, itis possible to insure that both the combustion and product gases exitthe furnace at moderate temperatures, for example below 500° C. Thisprovides high thermal efficiency and moderate temperatures of connectingpiping and equipment.

The present invention can be used to carry out a wide variety ofdifferent endothermic reactions such as steam reforming of lighthydrocarbons, especially methane, ethane and natural gas, the pyrolysisof alkanes such as ethane and propane to their corresponding alkenes,ethylene and propylene, the water-gas shift reaction, and so forth. Suchprocesses are well known in the art.

Some of these processes can be carried out without a catalyst whileothers require or usually employ a suitable catalyst. Where a catalystis used, it should maintain sufficient activity over a long period oftime at the high bed temperatures encountered herein. It should bestrong enough to support the bed weight above it. It should have aparticle size which is small enough to properly fill the spaces betweenthe tubes but large enough to minimize pressure drop through the bed toan acceptable value. It should not sinter-bond excessively to itself orto the tubes upon long exposures at the high temperatures. A suitableform of nickel on alumina is one possible candidate, but other catalystsare also reported to be suitable.

For hydrogen production, either a high-temperature shift catalyst and/ora low-temperature shift catalyst can optionally be placed within thereactor in the zone where the process gas is cooling and this will causemost of the CO to react with excess H₂ O to form more H₂ with CO₂ as abyproduct (the so-called "water-gas shift" reaction).

Many modifications clan be made of the preferred embodiments of theinvention as described above. For example, the gaseous fuel and air flowpaths could be switched, if desired. Also, these flow paths need not beannuluses concentric with the reaction tubes as shown but may be anyarrangement which allows the fuel and air to be separately heated toabove the autoignition temperatures before being combined in thecombustion zone. Also, a separate heat generating means for eachreaction tube is not needed either, it being sufficient that enough heatis supplied from one or more heat generating means in the interior ofthe furnace to drive the endothermic reaction. In addition, thecombustion gases, on the one hand, and the endothermic reaction gases,on the other hand, could be made to flow cocurrently, rather thancountercurrently, if desired.

Still other modifications are possible. For example, the process fluidstream could be of many different types, including gases, boilingliquids, liquids, or slurries containing fine solids. Gas to liquidcondensation might also desirably occur in the coolest zone of thereactor. In addition, cold reactor preheat for start-up could beachieved alternatively by other means than an electric resistanceheater. For example, hot combustion gases could be introduced throughsupplementary nozzles in the reactor and circulated through the desiredregion. Also, many different types of thermal insulation might be usedinside the pressure vessel. In addition, the maximum temperature of thecombustion gases within the combustion tubes of the ceramic tubeembodiment and outside the tubes in the metallic reaction tubeembodiment may be varied by adjusting the fuel composition and the fueland air flow rates. Increasing the air flow rate progressively above thestoichiometric ratio will progressively lower the maximum localtemperatures. Steam additions to the fuel can also reduce maximumtemperatures.

Finally, if syngas is desired for ammonia synthesis, an appropriate(usually small) proportion of compressed air may be added to the naturalgas and steam, such that the product syngas will contain the desiredratio of H₂ to N₂ (usually 3:1). This air addition will react in thecatalyst bed during heatup, but will be low enough so as not to producean excessive local temperature rise in the bed. The overall reactionwill remain endothermic. This method for making ammonia syngas does notrequire the addition of any oxygen aside from the air itself, which is adesirable cost savings versus some competing processes which require theseparation of oxygen from the air.

All such modifications are intended to be included within the scope ofthe present invention, which is to be limited only by the followingclaims.

What is claimed is:
 1. An endothermic reaction apparatus for effectingan endothermic reaction, comprisinga vessel, said vessel including aninlet port for an endothermic reactant to be subjected to an endothermicreaction to convert the reactant to an endothermic product, an outletport for the endothermic product, and an exothermic reaction chamberbetween the inlet and outlet ports along the flow path of theendothermic product, a plurality of reaction tubes providing flowpassages between said inlet and outlet ports, said reaction tubesextending through said exothermic reaction chamber from a downstream endto an upstream end of said exothermic reaction chamber, first and secondsupply passages for separately supplying first and second exothermicreactants to said exothermic reaction chamber for exothermicallyreacting within said exothermic reaction chamber and for providing flowof exothermic reaction products in a direction going from said upstreamend to said downstream end of said exothermic reaction chamber, saidfirst and second supply passages passing through a preheating zonewithin said vessel wherein heat is transferred to said exothermicreactants from said endothermic reaction product for preheating theexothermic reactants prior to mixing and exothermically reacting and forcooling said endothermic reaction product, and a plurality of feed tubesrespectively associated with said reaction tubes and disposed to producean annular shroud of flame around each reaction tube, said feed tubeseach having an outlet end located at said upstream end of saidexothermic reaction chamber and oriented to direct at least one of theexothermic reactants exiting therefrom in a direction substantiallyparallel to said reaction tubes such that the annular shroud of flame isdirected countercurrent to the flow of the endothermic reaction product.2. The endothermic reaction apparatus of claim 1, wherein said first andsecond supply passages pass through said preheating zone in such amanner that said exothermic reactants are heated sufficiently so as toautoignite when mixed together in said exothermic reaction chamber. 3.The endothermic reaction apparatus of claim 1, including an endothermicreaction catalyst in said reaction tubes.
 4. The endothermic reactionapparatus of claim 1, including a plurality of supply tubes, said supplytubes and respective reaction tubes being disposed one inside the otherand forming therebetween said first and second supply passages.
 5. Theendothermic reaction apparatus of claim 1, wherein said reaction tubeseach has a downstream portion disposed downstream of said exothermicreaction chamber in the direction of flow of endothermic product to saidoutlet port, and wherein there is provided a plurality of first supplytubes through which said downstream portions of said reaction tubescoextend, said first supply tubes and respective reaction tubes formingtherebetween one of said first and second supply passages in heatexchange relationship with said downstream portions of said reactiontubes.
 6. The endothermic reaction apparatus of claim 5, including aplurality of second supply tubes through which said first supply tubesrespectively coextend, and said first and respective second supply tubesforming therebetween an other of said first and second supply passagesin heat exchange relationship with said one of said first and secondsupply passages.
 7. The endothermic reaction apparatus of claim 1,wherein said reaction tubes are straight and parallel.
 8. Theendothermic reaction apparatus of claim 1, wherein said inlet for theendothermic reactant is at a first end of said vessel, said outlet forthe endothermic reaction product is at a second end of said vesselopposite said first end, said vessel includes first and second inletslocated at said second end of said vessel and respectively connected tosaid first and second supply passages, and an exhaust outlet located atsaid first end of said vessel and connected to said downstream end ofsaid exothermic reaction chamber.
 9. The endothermic reaction apparatusof claim 1, wherein said vessel is elongated and said reaction tubes andsaid exothermic reaction chamber extend longitudinally through saidvessel.
 10. The endothermic reaction apparatus of claim 1, comprisingmeans for causing the exothermic reaction products exiting from saidexothermic reaction chamber to flow around and along an upstream portionof each reaction tube located at the downstream end of the exothermicreaction chamber at a velocity substantially greater than the velocityof the exothermic reaction products through said exothermic reactionchamber to enhance heat transfer from said exothermic reaction productsto said upstream portion of each reaction tube for heating theendothermic reactant flowing through said upstream portion of eachreaction tube, said means for causing including an exhaust tube throughwhich said upstream portion of the respective reaction tube coextends,said exhaust tube and upstream portion of the reaction tube formingtherebetween an exhaust passage for the exothermic reaction products.11. The endothermic reaction apparatus of claim 1, wherein said vesselincludes an inlet manifold connected to said inlet port and an outletmanifold connected to said outlet port, and said reaction tubes providerespective flow passages between said inlet and outlet manifolds, saidreaction tubes extending through said exothermic reaction chamber inlaterally spaced apart relationship.
 12. The endothermic reactionapparatus of claim 11, wherein said first and second supply passagesinclude a plurality of supply passages having respective first andsecond fluid outlets disposed around said reaction tubes for introducingsaid first and second exothermic reactants into said exothermic reactionchamber.
 13. A process for carrying out an endothermic reaction in anendothermic reaction apparatus in which an endothermic reactant isheated by exothermic reaction of two exothermic reactants to therebyconvert the endothermic reactant into an endothermic product,comprisingcausing the endothermic reactant to flow through a pluralityof reaction tubes wherein the endothermic reactant is to undergo theendothermic reaction, the reaction tubes extending through an exothermicreaction chamber of a vessel from a downstream end to an upstream end ofsaid exothermic reaction chamber, removing the endothermic reactionproduct from said vessel after flow through said reaction tubes,separately supplying first and second exothermic reactants to saidexothermic reaction flow path for reacting within said exothermicreaction chamber with the exothermic reaction products flowing in adirection going from the upstream end to the downstream end of saidexothermic reaction chamber, and directing the first and secondexothermic reactants into the exothermic reaction chamber forexothermically reacting and producing an annular shroud of flame aroundeach reaction tube, said directing of one of the first and secondexothermic reactants being effected by a plurality of feed tubes eachhaving an outlet end located at the upstream end of the exothermicreaction chamber and oriented to direct such one exothermic reactionfluid exiting therefrom in a direction substantially parallel to saidreaction tubes such that the annular shroud of flame is directedcountercurrent to the flow of the endothermic reaction product, removingthe exothermic reaction products from said vessel after passage throughsaid exothermic reaction chamber, and wherein said separately supplyingstep includes passing the first and second exothermic reactants througha preheating zone within said vessel wherein heat is transferred to saidexothermic reactants from said endothermic reaction product forpreheating the exothermic reactants prior to mixing and reacting and forcooling said endothermic reaction product prior to removal from saidvessel.
 14. The endothermic reaction process of claim 13, wherein saidfirst and second exothermic reactants are heated sufficiently so as toautoignite when mixed together in said exothermic reaction chamber. 15.The endothermic reaction process of claim 13, wherein an endothermicreaction catalyst is used in said reaction tubes.
 16. The endothermicreaction process of claim 13, wherein one of said exothermic reactantsis passed through an annular passage formed between a downstream portionof each reaction tube in the direction of the flow of said endothermicproduct and a respective supply tube for transfer of heat from saidendothermic reaction product to said one of said exothermic reactants toheat the same prior to being mixed and reacted with the other of saidexothermic reactants.
 17. The endothermic reaction process of claim 16,wherein the other of said exothermic reactants is passed through anannular passage formed between said one supply tube and another supplytube for transfer of heat from said endothermic reaction product to saidexothermic reactants to heat the same prior to being mixed and reactedwith one another.
 18. The endothermic reaction process of claim 13,wherein said plurality of reaction tubes are straight and parallel. 19.The endothermic reaction process of claim 13, wherein the endothermicreactant and reaction product flow countercurrently to the exothermicreactants and reaction products.
 20. The endothermic reaction process ofclaim 19, wherein the vessel is elongated and the endothermic reactantand reaction product flow in a first longitudinal direction and theexothermic reactants and reaction products flow in a second longitudinaldirection opposite said first longitudinal direction.
 21. Theendothermic reaction process of claim 13, wherein the difference betweenthe temperature of said exothermic reactants prior to mixing and themaximum endothermic reaction temperature is less than 200 degrees C. 22.An apparatus for carrying out an endothermic reaction in which anendothermic reactant gas is heated by the combustion of air and acombustible fuel gas thereby to cause the reactant gas to form anendothermic product, which apparatus comprises:vessel; a plurality ofmetallic reaction tubes in the vessel dividing the interior of thevessel into a plurality of separate reaction tube flow pathscollectively defining a reaction flow path for carrying out theendothermic reaction and a plurality of separate elongated flame flowpaths outside the reaction tubes collectively defining a combustion flowpath, the reaction flow path and the combustion flow path being inthermal communication with one another so that heat in the combustionflow path can be transferred to the reaction flow path; respective heatgenerating means associated with each of the metallic reaction tubes forgenerating heat by the combustion of fuel gas and air with the resultantflames forming annular shrouds of flames around and extending along thereaction tubes; an inlet port for causing the reactant gas to flow intothe reaction flow path and an exit port for withdrawing endothermicproduct gas from the reaction flow path; air and fuel gas suppliesrespectively adapted to separately supply air and fuel gas to each ofthe heat generating means, the heat generating means being located inthe interior of the vessel whereby the air and fuel gas can be heated toabove their autoignition temperature prior to reaching the heatgenerating means; and an exit path for withdrawing combustion gas fromthe combustion flow path; and wherein the heat generating means arelocated at an upstream end of a combustion chamber in the vessel throughwhich the metallic reaction tubes extend from a downstream end to theupstream end of the combustion chamber, and the heat generating meansinclude a plurality of feed tubes respectively associated with themetallic reaction tubes, the feed tubes each having an outlet endlocated at the upstream end of the combustion chamber and oriented todirect the fuel gas exiting therefrom in a direction substantiallyparallel to the metallic reaction tubes such that the annular shroud offlame is directed countercurrent to the flow of the reactantgas/endothermic product.
 23. An apparatus as set forth in claim 22,wherein the air and gas fuel supplies respectively include a fuel gasfeed passageway and an air feed passageway for each tube, the associatedair feed passageway and fuel gas feed passageway for each tube beingconcentric.
 24. An apparatus as set forth in claim 22, wherein thereaction tubes contain endothermic reaction catalyst.
 25. An apparatusas set forth in claim 22, wherein the vessel is in the form of a shelland the reaction tubes are arranged in the form of a tube heat exchangerhaving a fixed tube sheet design.
 26. An apparatus as set forth in claim22, wherein the reaction tubes are unsupported intermediate theirrespective ends.
 27. An apparatus as set forth in claim 22, wherein thereaction tubes are essentially straight and essentially parallel.
 28. Aprocess for carrying out an endothermic reaction in an endothermicreaction apparatus in which an endothermic reactant gas is heated by thecombustion of air and a combustible fuel gas to thereby convert thereactant gas into an endothermic product, the apparatus including:avessel; a plurality of metallic reaction tubes in the vessel dividingthe interior of the vessel into a plurality of separate reaction tubeflow paths collectively defining a reaction flow path for carrying outthe endothermic reaction and a plurality of separate elongated flameflow paths outside the reaction tubes collectively defining a combustionflow path, the reaction flow path and the combustion flow path being inthermal communication with one another so that heat in the combustionflow path can be transferred to the reaction flow path; respective heatgenerating means associated with each of the metallic reaction tubes forgenerating heat by the combustion of fuel gas and air with the resultantflames forming annular shrouds of flames around and extending along thereaction tubes; an inlet port for causing the reactant gas to flow intothe reaction flow path an exit port for withdrawing endothermic productgas from the reaction flow path; and air and fuel gas suppliesrespectively adapted to separately supply air and fuel gas to each ofthe heat generating means, the heat generating means being located inthe interior of the vessel whereby the air and fuel gas can be heated toabove their autoignition temperature prior to reaching the heatgenerating means, and an exit path for withdrawing combustion gas fromthe combustion flow path; and wherein the heat generating means arelocated at an upstream end of a combustion chamber in the vessel throughwhich the metallic reaction tubes extend from a downstream end to theupstream end of the combustion chamber, and the heat generating meansinclude a plurality of feed tubes respectively associated with themetallic reaction tubes, the feed tubes each having an outlet endlocated at the upstream end of the combustion chamber and oriented todirect the fuel gas exiting therefrom in a direction substantiallyparallel to the metallic reaction tubes such that the annular shroud offlame is directed countercurrent to the flow of the reactantgas/endothermic product; the method comprising: via the inlet portcausing the endothermic reactant gas to flow along the endothermicreactant flow paths, via the air and fuel gas supplies separatelyfeeding the air and the fuel gas to each of the heat generating means,the fuel gas and air being heated to above their autoignitiontemperature prior to reaching the heat generating means so that the airand fuel gas autoignite and combust to produce heat in the combustionflow path with the resultant flames forming annular shrouds of flamesaround and extending along the reaction tubes, the heat beingtransferred to the endothermic reaction flow paths thereby causing theendothermic reaction to occur, via the outlet port withdrawingendothermic product gas from the reaction flow path, and via the exitpath withdrawing combustion gas from the combustion flow path.
 29. Aprocess according to claim 28, wherein the reaction tubes contain anendothermic reaction catalyst.
 30. A process as set forth in claim 28,wherein the endothermic reactant gas is a mixture of a gaseoushydrocarbon and steam whereby the endothermic product is synthesis gas.31. A process as set forth in claim 30, wherein the gaseous hydrocarbonis methane.
 32. A process as set forth in claim 30, wherein theendothermic reactant gas is heated to a temperature in the range 800 to1000° C.
 33. A process as set forth in claim 30, wherein the pressure inthe reaction flow paths is at least 0.508 mPa (10 atm.).